EP3886190A1 - Flexible and lightweight diode and its process of manufacturing - Google Patents
Flexible and lightweight diode and its process of manufacturing Download PDFInfo
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- EP3886190A1 EP3886190A1 EP20382214.3A EP20382214A EP3886190A1 EP 3886190 A1 EP3886190 A1 EP 3886190A1 EP 20382214 A EP20382214 A EP 20382214A EP 3886190 A1 EP3886190 A1 EP 3886190A1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/20—Organic diodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/80—Constructional details
- H10K10/82—Electrodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
Definitions
- the invention relates to a flexible and lightweight diode susceptible of being processed by inkjet printing additive manufacturing, which is based on conductive nanopaper. Furthermore, the invention relates to its process of manufacturing by means of an additive manufacturing technique and to an electronic component comprising said diode.
- the present invention could be included in the field of paper-based green electronics.
- a diode is a semiconductor device characterized by a rectifying interface which blocks or allows the current through it depending on the applied bias. It can be fabricated using broad architectures and organic materials processed from solution. Typical diode architectures are based on P-N or Schottky junctions where p-type/n-type organic semiconductor (OSC) or metal/OSC are the rectifying interfaces, respectively. P-N junctions require the use of two kinds of semiconductors with different type of majority charge carriers and to align the electrodes Work Function (WF) to the P-N semiconductor WF to obtain the formation of ohmic contacts. It should be further noted that the inherent diffusion of the majority charge carriers provokes a built-in potential of typically 0.7eV, thereby the devices start to operate above this potential.
- OSC p-type/n-type organic semiconductor
- metal/OSC metal/OSC
- Another aspect that has to be taken into account is that, in semiconductor devices, especially flexible organic diodes, a substantial portion of non-biodegradable solid waste is represented by plastic substrates.
- the invention refers to a flexible and lightweight diode, which can be included within the term paper-based green electronics.
- the diode of the present invention is based on a conductive nanopaper being therefore a sustainable, biodegradable and eco-friendly electronic component.
- the conductive nanopaper is acting as both, substrate and cathode.
- the first aspect of the present invention refers to a diode (herein “the diode of the present invention") susceptible of being processed by inkjet printing additive manufacturing characterized in that it comprises:
- the diode of the present invention is characterized by a high mechanical response, with a tensile strength of about 200 MPa and Young's modulus of about 13 GPa; and it is flexible, which means that the substrate is foldable in around 180 degrees and the organic semiconductor can maintain its properties under a strain of up to 0.62%.
- the diode of the present invention is lightweight, this means that its density is kept below 1.2 g cm -1 .
- the conductive nanopaper is acting as conductive substrate and as cathode, forming an ohmic contact with the first layer comprising a polymeric insulator.
- the substrate of the present invention is a conductive substrate which, at the same time, holds the devices and acts as cathode, becoming an active component of the diode. This is possible thanks to the fact that the rectifying characteristic arises from the first layer of a polymeric insulator/second layer of organic p-type semiconductor interface (insulator/OSC interface), releasing the cathode from being responsible of the rectification.
- insulator/OSC interface organic p-type semiconductor interface
- the conductive substrate of the diode of the present invention is a conductive nanopaper comprising:
- the conductive substrate consists of a conductive nanopaper, said conductive nanopaper consists of:
- the proposed invention allows to skip the deposition of the cathode onto non-functional substrates and of an eventual additional planarization layer on the substrate, allowing a reduction in material, time, and cost consumption.
- the conductive polymer of the conductive substrate is selected from poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and polypyrrole (PPy).
- the first layer of the diode of the present invention comprises a polymeric insulator.
- the polymeric insulator of the first layer is an ink comprising amorphous silica, epoxy resin and epoxy hardener.
- the second layer of the diode of the present invention comprises an organic p-type semiconductor (OSC).
- OSC organic p-type semiconductor
- PTAA poly(triaryl amine)
- the third layer of the diode of the present invention is acting as anode.
- the third layer is a metal layer, wherein the metal is selected from Ag and Au.
- the third layer is a polymeric layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS).
- the interface between the first layer comprising a polymeric insulator and the second layer comprising an organic p-type semiconductor is responsible for the rectifying characteristics of the diode of the present invention.
- the asymmetric characteristic of a diode is typically related to a change in its resistance, which is negligible in forward bias and high in reverse bias condition.
- OSCs usually favor only one type of carrier depending on the ease with which holes or electrons can be injected into said OSC from the electrodes.
- one of the multiple advantages of the present diode is that the work function (WF) of the organic p-type semiconductor (OSC) and the polymeric insulator do not need to be aligned.
- the main requirement for the diode of the present invention comes from the leakage behaviour of the polymeric insulator.
- the polymeric insulator must be leaky enough to allow the current flow in forward bias, without leading to short-circuits. Since the majority of the organic p-type semiconductors (OSCs) present similar WFs compared to the ones of metallic inks, the formation of an ohmic contact at the OSC/electrode interface is totally feasible.
- the current flows through the diode of the present invention thanks to the presence of a leaky insulator.
- the roughness of an underneath layer affects the quality and performance of the subsequent one.
- conductive cellulose-based substrates are preferable candidates thanks to their higher roughnesses compared to common polymeric substrates.
- inkjet printed conductive electrodes (cathodes) onto the non-functional cellulose substrate would reduce the intrinsic and beneficial roughness of the cellulose
- a substrate comprising a conductive polymer and cellulose nanofibers preserves the roughness needed to perturbate the good performance of the insulator. This feature is paramount to highlight because up to date rough substrates were detrimental for the correct operation of electronic devices.
- diode is a diode-logic gate.
- Diode logic (DL) technology is the use of diodes to build Boolean logic gates. The most common application for DL is in Diode-Transistor Logic (DTL) integrated circuits. Diodes can perform switching and digital logic operations. Forward and reverse bias switch a diode between the low and high impedance states, respectively. So that it may serve as a switch. Logic Diodes can perform digital logic functions: "AND” and "OR”.
- the present invention also refers to the process for the manufacturing of the diode of the present invention (herein “the process of the invention”) by inkjet printing additive manufacturing technique in which organic materials and nanoparticle-based materials are allowed in the form of solution.
- Said process comprises a step of printing the first layer comprising a polymeric insulator onto the conductive substrate comprising conductive nanopaper by means of an additive manufacturing technique, preferably by means of inkjet printing additive manufacturing technique.
- a second aspect of the present invention refers to a process for the manufacturing of a diode of the present invention described above, characterized in that it comprises the following steps:
- the conductive substrate of step (a) is obtained by following the next steps:
- the last aspect of the present invention refers to an electronic component comprising the diode of the present invention described above. Therefore, the present diode of the invention can be part of integrated circuits or electronic systems as discrete device. Diodes along with other electronic components such as resistors, transistors, etc. can create electronic circuits with a particular function, as for example rectifiers, oscillators, among others.
- FIG. 1a shows a vertical section of the diodes of the present invention.
- the diodes are fabricated on a nanopaper of Cellulose NanoFibers (CNF) doped with a conductive polymer, as, for example, PEDOT:PSS. This component acts as both the substrate (1) and the bottom electrode-cathode of the diode.
- CNF Cellulose NanoFibers
- the first layer (2) is a polymeric insulator (amorphous silica, epoxy resin, or crosslinked polyvinylphenol) inkjet-printed onto the conductive nanopaper.
- a polymeric insulator amorphous silica, epoxy resin, or crosslinked polyvinylphenol
- the second layer (3) is of organic p-type semiconductor (OSC), as, for example, the amorphous OSC such as PTAA.
- OSC organic p-type semiconductor
- the third layer (4) is the second electrode-anode.
- Figure 1b shows an optical image of the diode.
- the numeration of the layers is the same as the one adopted in Figure 1a .
- Figure 2a shows the fabrication scheme of the diodes of the present invention.
- the first component of the diode to be fabricated is the conductive nanopaper that acts as both the substrate (1) and the bottom electrode-cathode.
- the preparation of cellulose nanofibers follows the TEMPO-mediated oxidation at basic pH described in with 5 mmol of NaClO until constant pH of 10. After TEMPO-oxidation, the cellulose suspension is filtered and washed five times with distilled water to remove all non-reacted reagents and free ions. After that, the cellulose suspension at about 1.1 wt% concentration is passed through a high-pressure homogenizer (NS1001L PANDA PLUS 2K_GEA), 3 times at each pressure of 300, 600 and 900 bars.
- the cellulose nanofiber is diluted to about 0.2 wt% concentration with distilled water, dispersed for 30 s by means of an ultra-turrax (IKA, GmbH& Co. KG, Germany) and sonicated, for 10 min at an amplitude of 60% in two equal intervals with a 2 min standby, using a Q700 sonicator.
- IKA ultra-turrax
- the conductive polymer is also diluted with distilled water to about 0.5 wt% and stirred for 5 min.
- the PEDOT:PSS suspensions is then added into the above CNF suspension with different proportions of CNF-PEDOT:PSS (50/50 and 80/20).
- the mixture is stirred for 1 h, filtered with a vacuum filter, and dried for 20 min at 85 °C under a pressure of 0.5 - 0.6 bar using a Rapid Köthen sheet dryer.
- the first layer (2) of the diode is inkjet printed using a Fujifilm Dimatix DMP2831 desktop inkjet printer.
- polymeric insulator of the first layer (2) amorphous silica, epoxy resin, and crosslinked polyvinylphenol has been tested.
- Polymeric insulator of the first layer (2) is printed onto the conductive nanopaper. Different curing steps can be adopted according to the chosen polymeric insulator (2).
- the third layer (3) is an organic p-type semiconductor like the amorphous the organic p-type semiconductor poly(triaryl amine) (PTAA), is deposited on the top of the polymeric insulator of the first layer (2) using drop casting (0.1 ⁇ L). The curing process is performed on a hot plate for 2 minutes at 100 °C.
- the second electrode-anode is the third layer (4), for example, a silver conductive paste deposited by means of drop casting and dried in air.
- Figure 2b shows an optical image (i) and a SEM (image (ii) of the diode.
- the numeration of the layers is the same as the one adopted in Figure 2a .
- Figure 3 shows the electrical characterization of the diode.
- Figure 3a shows the typical rectifying behavior of the presented diode.
- the rectifier barrier is located at the insulator/semiconductor interface.
- the Rectification Ratio is defined as the ratio of the maximum forward bias current to the maximum reverse bias current at the same voltage.
- the diode reported in Figure 3a presents a RR of 1250.
- Figure 3b shows the capacitance-voltage and loss-voltage characteristics of the diode.
- the loss is the defined as the inverse of ⁇ R where ⁇ is the angular frequency and R is the resistance.
- ⁇ is the angular frequency
- R is the resistance.
- depletion and accumulation region can be distinguished, however, it is possible to notice how the loss keeps increasing as the capacitance increases and fails to saturate. This indicates the presence of a leaky insulator which is confirmed by the impedance characterization: the impedance value passes from 840 M ⁇ to 510 M ⁇ in the accumulation regime.
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention relates to a flexible and lightweight diode susceptible of being processed by inkjet printing additive manufacturing which is based on conductive nanopaper. Furthermore, the invention relates to its process of manufacturing by means of an additive manufacturing technique and to an electronic component comprising said diode. Therefore, the present invention could be included in the field of paper-based green electronics.
Description
- The invention relates to a flexible and lightweight diode susceptible of being processed by inkjet printing additive manufacturing, which is based on conductive nanopaper. Furthermore, the invention relates to its process of manufacturing by means of an additive manufacturing technique and to an electronic component comprising said diode.
- Therefore, the present invention could be included in the field of paper-based green electronics.
- In recent years, studies have been intensely made to develop organic and flexible diodes in which polymeric functional materials and temperature sensitive substrates such as plastic foils are employed.
- As a matter of definition herein, a diode is a semiconductor device characterized by a rectifying interface which blocks or allows the current through it depending on the applied bias. It can be fabricated using broad architectures and organic materials processed from solution. Typical diode architectures are based on P-N or Schottky junctions where p-type/n-type organic semiconductor (OSC) or metal/OSC are the rectifying interfaces, respectively. P-N junctions require the use of two kinds of semiconductors with different type of majority charge carriers and to align the electrodes Work Function (WF) to the P-N semiconductor WF to obtain the formation of ohmic contacts. It should be further noted that the inherent diffusion of the majority charge carriers provokes a built-in potential of typically 0.7eV, thereby the devices start to operate above this potential.
- As a consequence, considering:
- the lack of electrical stability of n-type OSCs,
- the need to control and balance the level of dopants of each semiconductor in P-N junctions,
- the need to align the electrodes WF to the P-N semiconductor WF to obtain the formation of ohmic contacts,
- The development of solution-based electronic components offers the possibility to manufacture flexible and lightweight electronics using additive processes. Inkjet printing, in particular, has been receiving growing interest as a method for the deposition of functional materials, as opposed to more conventional approaches. Although this technique has been widely used for the fabrication of flexible organic devices, so far, a simple diode still remains a challenge for the technology.
- To date, the related art has failed to effectively fabricate an organic Schottky diode using polymeric materials by means of inkjet printing onto temperature sensitive substrates. The low availability of solution-based metals with uneven WFs required to obtain a rectifier interface, hampers the implementation of diodes into large area manufacturing such as additive fabrication techniques. Although few metallic inks are commercially available and feature these characteristics, these materials often need the application of aggressive post-treatments, such as intense pulsed light (IPL) sintering or high curing temperatures among others, making them incompatible with OSCs and temperature sensitive substrates, as plastic or cellulose substrates. Evaporation and sputtering are still the most common techniques for the deposition of metal electrodes in the fabrication of organic diodes.
- All these requirements make difficult a rapid implementation of organic diodes into real applications; therefore, it would be advantageous to overcome these limitations.
- Another aspect that has to be taken into account is that, in semiconductor devices, especially flexible organic diodes, a substantial portion of non-biodegradable solid waste is represented by plastic substrates.
- Thus, it is needed to develop novel diodes that are able to face and overcome all the issues presented so far.
- The invention refers to a flexible and lightweight diode, which can be included within the term paper-based green electronics. The diode of the present invention is based on a conductive nanopaper being therefore a sustainable, biodegradable and eco-friendly electronic component. In the diode of the present invention the conductive nanopaper is acting as both, substrate and cathode.
- The first aspect of the present invention refers to a diode (herein "the diode of the present invention") susceptible of being processed by inkjet printing additive manufacturing characterized in that it comprises:
- a conductive substrate comprising a conductive nanopaper, said conductive nanopaper comprising:
- ∘ cellulose nanofibers in a weight percent of between 50 wt% and 80 wt% with respect to the total weight of the conductive substrate, and
- ∘ a conductive material in a weight percent of between 20 wt% and 50 wt% with respect to the total weight of the conductive substrate, said conductive material selected from a conductive polymer, carbon nanotubes or a combination thereof,
- a first layer comprising a polymeric insulator located onto the substrate, wherein the thickness of said first layer (2) is ranging between 500 nm and 1 µm ,
- a second layer comprising an organic p-type semiconductor (OSC) located onto the first layer, wherein the thickness of said second layer is ranging between 200 nm and 500 nm,
- a third layer located onto the second layer, wherein the thickness of said third layer is ranging between 100 nm and 200 nm,
- The diode of the present invention is characterized by a high mechanical response, with a tensile strength of about 200 MPa and Young's modulus of about 13 GPa; and it is flexible, which means that the substrate is foldable in around 180 degrees and the organic semiconductor can maintain its properties under a strain of up to 0.62%.
- The diode of the present invention is lightweight, this means that its density is kept below 1.2 g cm-1.
- In the present invention the conductive nanopaper is acting as conductive substrate and as cathode, forming an ohmic contact with the first layer comprising a polymeric insulator.
- The substrate of the present invention is a conductive substrate which, at the same time, holds the devices and acts as cathode, becoming an active component of the diode. This is possible thanks to the fact that the rectifying characteristic arises from the first layer of a polymeric insulator/second layer of organic p-type semiconductor interface (insulator/OSC interface), releasing the cathode from being responsible of the rectification.
- The conductive substrate of the diode of the present invention is a conductive nanopaper comprising:
- cellulose nanofibers in a weight percent of between 50 wt% and 80 wt% with respect to the total weight of the conductive substrate (1), and
- a conductive material in a weight percent of between 20 wt% and 50 wt% with respect to the total weight of the conductive substrate (1), said conductive material selected from a conductive polymer, carbon nanotubes or a combination thereof,
- In a preferred embodiment of the diode of the present invention the conductive substrate consists of a conductive nanopaper, said conductive nanopaper consists of:
- cellulose nanofibers in a weight percent of between 50 wt% and 80 wt% with respect to the total weight of the conductive substrate, and
- a conductive material in a weight percent of between 20 wt% and 50 wt% with respect to the total weight of the conductive substrate, said conductive material selected from a conductive polymer, carbon nanotubes or a combination thereof,
- The proposed invention allows to skip the deposition of the cathode onto non-functional substrates and of an eventual additional planarization layer on the substrate, allowing a reduction in material, time, and cost consumption.
- In a preferred embodiment of the diode of the present invention, the conductive polymer of the conductive substrate is selected from poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and polypyrrole (PPy).
- The first layer of the diode of the present invention comprises a polymeric insulator. Preferably, the polymeric insulator of the first layer is an ink comprising amorphous silica, epoxy resin and epoxy hardener.
- The second layer of the diode of the present invention comprises an organic p-type semiconductor (OSC). Preferably, the organic p-type semiconductor (OSC) of the second layer is poly(triaryl amine) (PTAA).
- The third layer of the diode of the present invention is acting as anode.
- In a preferred embodiment of the diode of the present invention, the third layer is a metal layer, wherein the metal is selected from Ag and Au.
- In another preferred embodiment of the diode of the present invention the third layer is a polymeric layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS).
- As mentioned before, the interface between the first layer comprising a polymeric insulator and the second layer comprising an organic p-type semiconductor (insulator/OSC interface) is responsible for the rectifying characteristics of the diode of the present invention. The asymmetric characteristic of a diode is typically related to a change in its resistance, which is negligible in forward bias and high in reverse bias condition. OSCs usually favor only one type of carrier depending on the ease with which holes or electrons can be injected into said OSC from the electrodes.
- Two different regimes of operation can be distinguished in the diode of the present invention: accumulation and depletion, defined according to the effect that the applied voltage has on the p-type OSC.
- Under the application of a positive voltage to the hole transport p-type OSC semiconductor, free charges are injected and accumulated at the insulator/OSC interface (accumulation region). If a high conductance is registered across the insulator, the accumulation capacitance does not saturate, and a certain amount of current can pass through the insulator (forward bias).
- Conversely, when a negative bias is applied to the organic p-type semiconductor (OSC), charges accumulate at the third layer (anode) electrode/ organic p-type semiconductor (OSC) interface. Thus, there is no charge at the polymeric insulator/ organic p-type semiconductor (OSC) interface, leaving only a space charge or depletion layer (reverse bias). The reverse leakage current and forward current give indications about the depletion region and accumulation region at the interface between the organic p-type semiconductor (OSC) and the polymeric insulator.
- Therefore, one of the multiple advantages of the present diode is that the work function (WF) of the organic p-type semiconductor (OSC) and the polymeric insulator do not need to be aligned. The main requirement for the diode of the present invention comes from the leakage behaviour of the polymeric insulator. The polymeric insulator must be leaky enough to allow the current flow in forward bias, without leading to short-circuits. Since the majority of the organic p-type semiconductors (OSCs) present similar WFs compared to the ones of metallic inks, the formation of an ohmic contact at the OSC/electrode interface is totally feasible.
- As stated before, the current flows through the diode of the present invention thanks to the presence of a leaky insulator. As it is known, the roughness of an underneath layer affects the quality and performance of the subsequent one. Based on that, conductive cellulose-based substrates are preferable candidates thanks to their higher roughnesses compared to common polymeric substrates. Whereas inkjet printed conductive electrodes (cathodes) onto the non-functional cellulose substrate would reduce the intrinsic and beneficial roughness of the cellulose, a substrate comprising a conductive polymer and cellulose nanofibers preserves the roughness needed to perturbate the good performance of the insulator. This feature is paramount to highlight because up to date rough substrates were detrimental for the correct operation of electronic devices.
- In another preferred embodiment of the diode of the invention said diode is a diode-logic gate. Diode logic (DL) technology is the use of diodes to build Boolean logic gates. The most common application for DL is in Diode-Transistor Logic (DTL) integrated circuits. Diodes can perform switching and digital logic operations. Forward and reverse bias switch a diode between the low and high impedance states, respectively. So that it may serve as a switch. Logic Diodes can perform digital logic functions: "AND" and "OR".
- The present invention also refers to the process for the manufacturing of the diode of the present invention (herein "the process of the invention") by inkjet printing additive manufacturing technique in which organic materials and nanoparticle-based materials are allowed in the form of solution. Said process comprises a step of printing the first layer comprising a polymeric insulator onto the conductive substrate comprising conductive nanopaper by means of an additive manufacturing technique, preferably by means of inkjet printing additive manufacturing technique.
- Therefore, a second aspect of the present invention refers to a process for the manufacturing of a diode of the present invention described above, characterized in that it comprises the following steps:
- a) printing the first layer onto the conductive substrate by means of an additive manufacturing technique, preferably by means of inkjet printing,
- b) curing the product obtained in step (a), preferably by means of a hot plate,
- c) drop casting of the second layer onto the cured product obtained in step (b),
- d) curing the product obtained in step (c), preferably by means of a hot plate,
- e) drop casting of the third layer onto the cured product obtained in step (d), and f) drying the product obtained in step (e) in air.
- In a preferred embodiment of the process of the invention the conductive substrate of step (a) is obtained by following the next steps:
- i) mixing a solution of cellulose nanofibers and a solution of a conductive material selected from a conductive polymer, carbon nanotubes or a combination thereof, wherein the weight percent of the cellulose nanofibers is ranging between 50 wt% and 80 wt% and the weight percent of the conductive material is ranging between 20 wt% and 50 wt% in the final mixture, and
- ii) filtering the mixed obtained in step (i) under vacuum at a pressure ranging from 0.1 bar to 0.9 bar and at a temperature between 30 °C and 100 °C.
- The last aspect of the present invention refers to an electronic component comprising the diode of the present invention described above. Therefore, the present diode of the invention can be part of integrated circuits or electronic systems as discrete device. Diodes along with other electronic components such as resistors, transistors, etc. can create electronic circuits with a particular function, as for example rectifiers, oscillators, among others.
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Figure 1 . Scheme of the diode multilayered structure of the present invention (a). Optical images of the diode (b). -
Figure 2 . Fabrication scheme of the diode structures (a). Optical (i) and SEM images (ii) of a fabricated diode (b). -
Figure 3 . Electrical characterization of the diodes. I-V characteristics in linear scale (left axis) and semi-logarithmic scale (right axis) (a) Capacitance-Voltage (left axis) and Loss-Voltage (right axis) characteristics (b). -
Figure 1a shows a vertical section of the diodes of the present invention. The diodes are fabricated on a nanopaper of Cellulose NanoFibers (CNF) doped with a conductive polymer, as, for example, PEDOT:PSS. This component acts as both the substrate (1) and the bottom electrode-cathode of the diode. - The first layer (2) is a polymeric insulator (amorphous silica, epoxy resin, or crosslinked polyvinylphenol) inkjet-printed onto the conductive nanopaper.
- The second layer (3) is of organic p-type semiconductor (OSC), as, for example, the amorphous OSC such as PTAA.
- The third layer (4) is the second electrode-anode.
-
Figure 1b shows an optical image of the diode. The numeration of the layers is the same as the one adopted inFigure 1a . -
Figure 2a shows the fabrication scheme of the diodes of the present invention. - The first component of the diode to be fabricated is the conductive nanopaper that acts as both the substrate (1) and the bottom electrode-cathode.
- The preparation of cellulose nanofibers follows the TEMPO-mediated oxidation at basic pH described in with 5 mmol of NaClO until constant pH of 10. After TEMPO-oxidation, the cellulose suspension is filtered and washed five times with distilled water to remove all non-reacted reagents and free ions. After that, the cellulose suspension at about 1.1 wt% concentration is passed through a high-pressure homogenizer (NS1001L PANDA PLUS 2K_GEA), 3 times at each pressure of 300, 600 and 900 bars.
- For the preparation of the conductive nanopaper, the cellulose nanofiber is diluted to about 0.2 wt% concentration with distilled water, dispersed for 30 s by means of an ultra-turrax (IKA, GmbH& Co. KG, Germany) and sonicated, for 10 min at an amplitude of 60% in two equal intervals with a 2 min standby, using a Q700 sonicator.
- For the fabrication of conductive nanopapers with PEDOT:PSS as the conductive polymer, the conductive polymer is also diluted with distilled water to about 0.5 wt% and stirred for 5 min. The PEDOT:PSS suspensions is then added into the above CNF suspension with different proportions of CNF-PEDOT:PSS (50/50 and 80/20). The mixture is stirred for 1 h, filtered with a vacuum filter, and dried for 20 min at 85 °C under a pressure of 0.5 - 0.6 bar using a Rapid Köthen sheet dryer.
- The first layer (2) of the diode is inkjet printed using a Fujifilm Dimatix DMP2831 desktop inkjet printer. As polymeric insulator of the first layer (2) amorphous silica, epoxy resin, and crosslinked polyvinylphenol has been tested. Polymeric insulator of the first layer (2) is printed onto the conductive nanopaper. Different curing steps can be adopted according to the chosen polymeric insulator (2).
- The third layer (3) is an organic p-type semiconductor like the amorphous the organic p-type semiconductor poly(triaryl amine) (PTAA), is deposited on the top of the polymeric insulator of the first layer (2) using drop casting (0.1 µL). The curing process is performed on a hot plate for 2 minutes at 100 °C. The second electrode-anode is the third layer (4), for example, a silver conductive paste deposited by means of drop casting and dried in air.
-
Figure 2b shows an optical image (i) and a SEM (image (ii) of the diode. The numeration of the layers is the same as the one adopted inFigure 2a . -
Figure 3 shows the electrical characterization of the diode.Figure 3a shows the typical rectifying behavior of the presented diode. The rectifier barrier is located at the insulator/semiconductor interface. - The Rectification Ratio (RR) is defined as the ratio of the maximum forward bias current to the maximum reverse bias current at the same voltage. The diode reported in
Figure 3a presents a RR of 1250. -
Figure 3b shows the capacitance-voltage and loss-voltage characteristics of the diode. The loss is the defined as the inverse of ωR where ω is the angular frequency and R is the resistance. InFigure 3b , depletion and accumulation region can be distinguished, however, it is possible to notice how the loss keeps increasing as the capacitance increases and fails to saturate. This indicates the presence of a leaky insulator which is confirmed by the impedance characterization: the impedance value passes from 840 MΩ to 510 MΩ in the accumulation regime.
Claims (12)
- A diode susceptible of being processed by inkjet printing additive manufacturing characterized in that it comprises:• a conductive substrate (1) comprising a conductive nanopaper, said conductive nanopaper comprising:∘ cellulose nanofibers in a weight percent of between 50 wt% and 80 wt% with respect to the total weight of the conductive substrate (1), and∘ a conductive material in a weight percent of between 20 wt% and 50 wt% with respect to the total weight of the conductive substrate (1), said conductive material selected from a conductive polymer, carbon nanotubes or a combination thereof,and wherein the thickness of said conductive substrate (1) is ranging between 20 µm and 200 µm,• a first layer (2) comprising a polymeric insulator located onto the substrate (1), wherein the thickness of said first layer (2) is ranging between 500 nm and 1 µm,• a second layer (3) comprising an organic p-type semiconductor located onto the first layer (2), wherein the thickness of said second layer (3) is ranging between 200 nm and 500 nm,• a third layer (4) located onto the second layer (3), wherein the thickness of said third layer (4) is ranging between 100 nm and 200 nm,and wherein the conductive substrate (1) is acting as cathode and the third layer (4) is acting as anode.
- The diode according to claim 1, wherein the conductive polymer of the conductive substrate (1) is selected from poly(3,4-ethylenedioxythiophene) polystyrene sulfonate and polypyrrole.
- The diode according to any of claims 1 or 2, wherein the polymeric insulator of the first layer (2) is an ink comprising amorphous silica, epoxy resin and epoxy hardener.
- The diode according to any of claims 1 to 3, wherein the organic p-type semiconductor of the second layer (3) is poly(triaryl amine).
- The diode according to any of claims 1 to 4, wherein the third layer (4) is a metal layer, and wherein the metal is selected from Ag and Au.
- The diode according to any of claims 1 to 4, wherein the third layer (4) is a polymeric layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate.
- The diode according to any of claims 1 to 6 is a diode-logic gate.
- A process for the manufacturing of a diode according to any of claims 1 to 7, characterized in that it comprises the following steps:a) printing the first layer (2) onto the conductive substrate (1) by means of an additive manufacturing technique,b) curing the product obtained in step (a),c) drop casting of the second layer (3) onto the cured product obtained in step (b),d) curing the product obtained in step (c), ande) drop casting of the third layer (4) onto the cured product obtained in step (d),f) drying the product obtained in step (e) in air.
- The process according to claim 8, wherein the conductive substrate (1) of step (a) is obtained by following the next steps:i) mixing a solution of cellulose nanofibers and a solution of a conductive material selected from a conductive polymer, carbon nanotubes or a combination thereof, wherein the weight percent of the cellulose nanofibers is ranging between 50 wt% and 80 wt% and the weight percent of the conductive material is ranging between 20 wt% and 50 wt% in the final mixture, andii) filtering the mixed obtained in step (i) under vacuum at a pressure ranging from 0.1 bar to 0.9 bar and at a temperature between 30 °C and 100 °C.
- The process according to any of claims 8 or 9, wherein step (a) is performed by means of inkjet printing.
- The process according to any of claims 8 to 10, wherein steps (b) and (d) are performed by means of a hot plate independently.
- Electronic component comprising the diode according to any of claims 1 to 7.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP20382214.3A EP3886190A1 (en) | 2020-03-23 | 2020-03-23 | Flexible and lightweight diode and its process of manufacturing |
PCT/EP2021/055927 WO2021190916A1 (en) | 2020-03-23 | 2021-03-09 | Flexible and lightweight diode and its process of manufacturing |
EP21709995.1A EP4128383A1 (en) | 2020-03-23 | 2021-03-09 | Flexible and lightweight diode and its process of manufacturing |
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EP20382214.3A EP3886190A1 (en) | 2020-03-23 | 2020-03-23 | Flexible and lightweight diode and its process of manufacturing |
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EP20382214.3A Withdrawn EP3886190A1 (en) | 2020-03-23 | 2020-03-23 | Flexible and lightweight diode and its process of manufacturing |
EP21709995.1A Pending EP4128383A1 (en) | 2020-03-23 | 2021-03-09 | Flexible and lightweight diode and its process of manufacturing |
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US20070096080A1 (en) * | 2003-07-02 | 2007-05-03 | Cain Paul A | Rectifying diodes |
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2021
- 2021-03-09 EP EP21709995.1A patent/EP4128383A1/en active Pending
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Patent Citations (1)
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US20070096080A1 (en) * | 2003-07-02 | 2007-05-03 | Cain Paul A | Rectifying diodes |
Non-Patent Citations (2)
Title |
---|
CARME MARTÍNEZ-DOMINGO ET AL: "Novel flexible inkjet-printed Metal-Insulator-Semiconductor organic diode employing silver electrodes", ORGANIC ELECTRONICS, vol. 62, 7 August 2018 (2018-08-07), NL, pages 335 - 341, XP055728255, ISSN: 1566-1199, DOI: 10.1016/j.orgel.2018.08.011 * |
GUSTAV NYSTROM ET AL: "A Nanocellulose Polypyrrole Composite Based on Microfibrillated Cellulose from Wood", THE JOURNAL OF PHYSICAL CHEMISTRY B, vol. 114, no. 12, 5 March 2010 (2010-03-05), pages 4178 - 4182, XP055027799, ISSN: 1520-6106, DOI: 10.1021/jp911272m * |
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EP4128383A1 (en) | 2023-02-08 |
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